agricultural additives

Abstract

To provide an agriculture addition agent which is more excellent in expansion properties and exhibits preferable dispersion stability.SOLUTION: The invention relates to an agriculture addition agent which is a copolymer formed of: 80-99 mass% of a polyalkylene glycol mono alkenyl ether monomer (I) expressed by a following general formula (1); 0.1-10 mass% of esterified monomer (II) of an unsaturated carboxylic acid and (poly)alkylene glycol expressed by a following general formula (2); 0.1-20 mass% of an unsaturated mono carboxylic acid based monomer (III); and 0-18 mass% of other monomer (IV) which can copolymerize to the monomers (I) to (III). The monomer (II) includes: a polycarboxylic acid based copolymer including a monomer (IIa) in which, n2 in the general formula (2) is 1-3, and a monomer (IIb) in which n2 in the general formula (2) is 4-100, in a range of (IIa) / (IIb)=60 / 40 to 99 / 1; or a salt of the polycarboxylic acid based copolymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to agricultural additives. [Background technology]

[0002] Polycarboxylic acid copolymers or salts thereof have excellent cement dispersibility and slump retention, and can reduce the viscosity of cement compositions and improve workability, and are therefore used as dispersants for cement and gypsum (for example, Patent Document 1).

[0003] On the other hand, granular pesticide formulations are becoming more widely used because they are easier to work with than powdered pesticide formulations. Important physical properties of granular pesticide formulations include disintegration and diffusibility. Disintegration is an indicator of how easily the granules disintegrate in water. When granular pesticide formulations are diluted with water to prepare a spray solution, the granules must disintegrate quickly in water. Furthermore, pesticides must be widely sprayed after disintegrating in water, and diffusibility is an indicator of their ability to diffuse far in water. Furthermore, some pesticide formulations are slurried with water before use. In this case, both diffusibility and slurry stability are required.

[0004] For example, Patent Document 2 describes that a water dispersible granule containing (a) an agricultural chemical active ingredient that is solid at 25°C, (b) a polyoxyalkylene alkyl ether phosphate or a salt thereof, (c) an arylsulfonate or its formaldehyde condensate, at least one anionic surfactant selected from the group consisting of lignin sulfonate and polycarboxylate, and (d) lactose does not deteriorate in disintegration in water even after two weeks of storage at 54°C. Furthermore, Patent Document 3 describes that a lignin derivative derived from a compound having a structural unit derived from a lignin compound and a polyalkylene oxide chain, and having a phenolic hydroxyl group content and an alkylene oxide addition mole number within a specified range, can improve the dispersibility of agricultural chemicals. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6343655 [Patent Document 2] International Publication No. 2014 / 133178 [Patent Document 3] International Publication No. 2021 / 066166 Summary of the Invention [Problem to be solved by the invention]

[0006] However, there are concerns that petroleum-derived agents such as those described in Patent Document 2 may cause unexpected soil contamination in agricultural land. Although lignin derivatives such as those described in Patent Document 3 can solve this problem, there is a demand for more versatile and high-performance agricultural chemical additives.

[0007] Therefore, in order to solve the above problems, an object of the present invention is to provide an agricultural chemical additive which has superior spreadability and exhibits good dispersion stability. [Means for solving the problem]

[0008] The present invention provides the following [1] to [8]. [1] 80 to 99% by weight of a monomer (I) represented by the following general formula (1), 0.1 to 10% by weight of a monomer (II) represented by the following general formula (2), 0.1 to 20% by weight of an unsaturated monocarboxylic acid monomer (III), and 0 to 18% by weight of other monomers (IV) copolymerizable with monomers (I) to (III) is a copolymer of The monomer (II) includes a monomer (IIa) in which n2 in the general formula (2) is 1 to 3 and a monomer (IIb) in which n2 in the general formula (2) is 4 to 100, the weight ratio of the monomer (IIa) to the monomer (IIb) ((IIa) / (IIb)) is in the range of 60 / 40 to 99 / 1; A pesticide additive containing a polycarboxylic acid copolymer or a salt thereof. [ka] (In the formula, R 1 represents the residue of an allyl group, a methallyl group, or 3-methyl-3-buten-1-ol. 1 O's are the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms. n1 is the average number of moles of oxyalkylene groups added and represents a number from 1 to 100. R2 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. [ka] (In the formula, R 3 , R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents a number from 0 to 2. A 2 O are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. n2 is the average number of moles of oxyalkylene groups added and represents a number from 1 to 100. X represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. [2] The ratio of the structure derived from monomer (III) to the structure derived from monomer (II) ( (III) / (II) ) is 35 to 99% by weight. [3] The agricultural additive according to [1] or [2], wherein the monomer (III) comprises acrylic acid or a salt thereof (IIIa) and methacrylic acid or a salt thereof (IIIb). [4] The pesticide additive according to [3], wherein the ratio ((IIIa) / (IIIb) of the structure derived from acrylic acid or a salt thereof (IIIa) to the structure derived from methacrylic acid or a salt thereof (IIIb) is (99% to 51%) / (1% to 49%). [5] The agricultural chemical additive according to any one of [1] to [4], which has a weight-average molecular weight of 10,000 to 50,000. [6] The agricultural chemical additive according to any one of [1] to [5], which has a molecular weight distribution of 1.2 to 3.0. [7] The pesticide additive according to any one of [1] to [6], which is for use in granular pesticides. [8] The pesticide additive according to any one of [1] to [6], which is for use in liquid pesticides. [Effects of the Invention]

[0009] According to the present invention, there is provided an agricultural chemical additive which has superior spreadability and good dispersion stability. DETAILED DESCRIPTION OF THE INVENTION

[0010] (1. Pesticide additives) The agricultural chemical additive contains a polycarboxylic acid copolymer or a salt thereof.

[0011] (1.1 Polycarboxylic acid copolymer) The polycarboxylic acid copolymer is a copolymer of the monomers (I) to (III) and, optionally, the monomer (IV). The polycarboxylic acid copolymer has a structural unit derived from the monomer (I), a structural unit derived from the monomer (II), a structural unit derived from the monomer (III), and a structural unit derived from the monomer (IV) that is optionally included.

[0012] -Monomer (I)- The monomer (I) is represented by the general formula (1): [ka] It is a polyalkylene glycol monoalkenyl ether represented by the formula:

[0013] R in general formula (1) 1 is the residue of an allyl group, a methallyl group or 3-methyl-3-buten-1-ol, preferably the residue of a methallyl group or 3-methyl-3-buten-1-ol.

[0014] A in general formula (1) 1O's may be the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group include an oxyethylene group (ethylene glycol), an oxypropylene group (propylene glycol), and an oxybutylene group (butylene glycol), with an oxyethylene group (ethylene glycol) and an oxypropylene group (propylene glycol) being preferred.

[0015] A 1 When multiple Os are contained in a monomer (when n1 is 2 or more), each A 1 O may be the same or different (two or more types) oxyalkylene groups. 1 Examples of compounds containing multiple O include a mixture of two or more oxyalkylene groups selected from the group consisting of oxyethylene groups (ethylene glycol), oxypropylene groups (propylene glycol), and oxybutylene groups (butylene glycol), with preferred embodiments including a mixture of oxyethylene groups (ethylene glycol) and oxypropylene groups (propylene glycol), or a mixture of oxyethylene groups (ethylene glycol) and oxybutylene groups (butylene glycol), and more preferred embodiments including a mixture of oxyethylene groups (ethylene glycol) and oxypropylene groups (propylene glycol). In embodiments including a mixture of different oxyalkylene groups, the addition of two or more types of oxyalkylene groups may be block-like or random.

[0016] In general formula (1), n1 is the average number of moles of oxyalkylene groups added. n1 is a number from 1 to 100, preferably from 1 to 90, more preferably from 5 to 80, even more preferably from 15 to 70, and still more preferably from 20 to 60. In this specification, the average number of moles added means the average value of the number of moles of alkylene glycol units added to 1 mole of monomer.

[0017] R in general formula (1) 2is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom or a methyl group. The hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic, but is preferably a saturated hydrocarbon group, and more preferably a linear saturated hydrocarbon group.

[0018] The monomer (I) can be produced, for example, by adding 1 to 80 moles of alkylene oxide to an unsaturated alcohol such as allyl alcohol, methallyl alcohol, or 3-methyl-3-buten-1-ol.

[0019] Examples of the monomer (I) include (poly)ethylene glycol allyl ether, (poly)ethylene glycol methallyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)propylene glycol allyl ether, (poly)ethylene (poly)propylene glycol methallyl ether, (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)butylene glycol allyl ether, (poly)ethylene (poly)butylene glycol methallyl ether, (poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene glycol Examples of suitable monomers include glycol allyl ether, methoxy(poly)ethylene glycol methallyl ether, methoxy(poly)ethylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)propylene glycol allyl ether, methoxy(poly)ethylene (poly)propylene glycol methallyl ether, methoxy(poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)butylene glycol allyl ether, methoxy(poly)ethylene (poly)butylene glycol methallyl ether, and methoxy(poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether. While one or more of these may be used as the monomer (I), it is preferable to use (poly)ethylene glycol (meth)allyl ether in view of the balance between hydrophilicity and hydrophobicity. In the specific examples of the monomer (I), the average number of moles of oxyalkylene groups (polyalkylene glycols) added is preferably 1 to 70, more preferably 5 to 70, and even more preferably 8 to 70. In this specification, "(poly)" means that the number of substituents immediately following it is one or two or more.

[0020] The monomer (I) may be one type or a combination of two or more types.

[0021] -Monomer (II)- The monomer (II) is represented by the following general formula (2): [ka] It is an ester of an unsaturated carboxylic acid represented by the formula (I) and a (poly)alkylene glycol.

[0022] R in general formula (2) 3 , R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0023] A in general formula (2) 2 O's may be the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group include an oxyethylene group (ethylene glycol), an oxypropylene group (propylene glycol), and an oxybutylene group (butylene glycol), with an oxyethylene group (ethylene glycol) and an oxypropylene group (propylene glycol) being preferred.

[0024] In general formula (2), A 2 If multiple Os are included (n2 is 2 or more), each A 2 O may be the same oxyalkylene group or different (two or more types of) oxyalkylene groups. 2 When multiple O's are contained, for example, two or more oxyalkylene groups selected from the group consisting of oxyethylene groups (ethylene glycol), oxypropylene groups (propylene glycol), and oxybutylene groups (butylene glycol) are present in combination. An embodiment in which an oxyethylene group (ethylene glycol) and an oxypropylene group (propylene glycol) are present in combination, or an embodiment in which an oxyethylene group (ethylene glycol) and an oxybutylene group (butylene glycol) are present in combination, is preferred, and an embodiment in which an oxyethylene group (ethylene glycol) and an oxypropylene group (propylene glycol) are present in combination is more preferred. In an embodiment in which different oxyalkylene groups are present in combination, the addition of two or more types of oxyalkylene groups may be in block addition or random addition.

[0025] In the general formula (2), n2 is the average number of moles of oxyalkylene groups added, which is a number from 1 to 100, preferably from 1 to 50, more preferably from 5 to 50, and even more preferably from 8 to 50.

[0026] X in general formula (2) is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom or a methyl group.

[0027] Examples of the monomer (II) include esters of unsaturated monocarboxylic acids such as (meth)acrylates (hereinafter, "(meth)acrylate" means "acrylate or methacrylate") with (poly)alkylene glycols such as (poly)ethylene glycol, (poly)ethylene (poly)propylene glycol, (poly)ethylene (poly)butylene glycol, methoxy(poly)ethylene glycol, methoxy(poly)ethylene (poly)propylene glycol, and methoxy(poly)ethylene (poly)butylene glycol. Specifically, for example, (poly)ethylene glycol (meth)acrylate, (poly)ethylene (poly)propylene glycol (meth)acrylate, (poly)ethylene (poly)butylene glycol (meth)acrylate, methoxy(poly)ethylene glycol (meth)acrylate, methoxy(poly)ethylene (poly)propylene glycol (meth)acrylate, methoxy(poly)ethylene (poly)butylene glycol (meth)acrylate, etc. are mentioned, (poly)alkylene glycol (meth)acrylate is preferred, (poly)ethylene glycol (meth)acrylate and methoxy(poly)ethylene glycol (meth)acrylate are more preferred. Further, other examples include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.

[0028] -Monomers (IIa) and (IIb)- The monomer (II) may be one type of monomer represented by general formula (2) or a combination of two or more types, preferably a combination of two or more types, and preferably includes at least a combination of two types of monomers (IIa) and (IIb) having different average molar numbers of oxyalkylene groups added.

[0029] Monomer (IIa) is a monomer whose average number of moles added, n2a, is smaller than the average number of moles added, n2b, of monomer (IIb). n2a is usually 1 to 3, more preferably 1 to 2, and even more preferably 1. n2b is usually 4 to 100, preferably 6 to 100, and more preferably 6 to 50. In the polycarboxylic acid copolymer or salt thereof (A), the ratio of the structure derived from monomer (IIa) to the structure derived from monomer (IIb) ((IIa) / (IIb)) is usually 60 / 40 to 99 / 1, preferably 70 / 30 to 99 / 1, and more preferably 80 / 20 to 99 / 1. The above ratio is usually the same as the amount of each monomer added when producing the copolymer.

[0030] Monomer (IIa) may be one or a combination of two or more monomers, and preferably includes a hydroxyalkyl (meth)acrylate. Monomer (IIb) may be one or a combination of two or more monomers, and preferably includes an ester of an unsaturated monocarboxylic acid with a (poly)alkylene glycol.

[0031] -Monomer (III)- Monomer (III) is an unsaturated monocarboxylic acid monomer. Examples of the unsaturated monocarboxylic acid monomer include carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and salts thereof (e.g., monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts), with acrylic acid, methacrylic acid, and salts thereof being preferred.

[0032] When the monomer (III) contains a combination of acrylic acid (salt) and methacrylic acid (salt), the ratio of the structure derived from acrylic acid (salt) (IIIa) to the structure derived from methacrylic acid (salt) (IIIb) in the polycarboxylic acid copolymer or salt (A) ((IIIa) / (IIIb): the total of IIIa and IIIb is 100% by weight) is preferably (99% to 51%) / (1% to 49%), more preferably (99% to 60%) / (1% to 40%), even more preferably (99% to 70%) / (80% to 30%), and even more preferably (99% to 80%) / (1% to 20%) or (99% to 90%) / (1% to 10%). The above ratio is usually the same as the amount of each monomer added when producing the copolymer.

[0033] The monomer (III) may be one type or a combination of two or more types.

[0034] -Monomer (IV)- Monomer (IV) is a monomer copolymerizable with at least one monomer selected from the group consisting of monomers (I), (II) and (III), and does not include monomers (I) to (III).

[0035] Examples of the monomer (IV) include the following compounds and combinations of two or more of these:

[0036] Diallyl bisphenols represented by the following general formula (IV-1), such as 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone allyl-substituted at the 3- and 3'-positions; [ka]

[0037] Monoallyl bisphenols represented by the following general formula (IV-2), such as 3-allyl-substituted 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone; [ka]

[0038] Allylphenol represented by the following general formula (IV-3): [ka]

[0039] Half esters and diesters of unsaturated dicarboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, with alcohols having 1 to 30 carbon atoms; Half amides and diamides of the above unsaturated dicarboxylic acids with amines having 1 to 30 carbon atoms; half esters and diesters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to the above alcohols or amines, and the above unsaturated dicarboxylic acids; half esters and diesters of the above unsaturated dicarboxylic acids with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of addition of these glycols; half amides of maleamic acid with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of addition of such glycols;

[0040] (poly)alkylene glycol di(meth)acrylates such as triethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and (poly)ethylene glycol (poly)propylene glycol di(meth)acrylate; polyfunctional (meth)acrylates such as hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane di(meth)acrylate; (Poly)alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate; unsaturated sulfonic acids such as vinyl sulfonate, (meth)allyl sulfonate, 2-(meth)acryloxyethyl sulfonate, 3-(meth)acryloxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfophenyl ether, 3-(meth)acryloxy-2-hydroxypropyloxysulfobenzoate, 4-(meth)acryloxybutyl sulfonate, (meth)acrylamidomethyl sulfonic acid, (meth)acrylamidoethyl sulfonic acid, 2-methylpropanesulfonic acid (meth)acrylamide, and styrenesulfonic acid, as well as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts; amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms, such as methyl (meth)acrylamide; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene; alkanediol mono(meth)acrylates such as 1,4-butanediol mono(meth)acrylate, 1,5-pentanediol mono(meth)acrylate, and 1,6-hexanediol mono(meth)acrylate; Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene;

[0041] unsaturated amides such as (meth)acrylamide, (meth)acrylalkylamide, N-methylol(meth)acrylamide, and N,N-dimethyl(meth)acrylamide; Unsaturated cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile; unsaturated esters such as vinyl acetate and vinyl propionate; unsaturated amines such as aminoethyl (meth)acrylate, methylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, and vinylpyridine; Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; Allyl compounds such as (meth)allyl alcohol and glycidyl (meth)allyl ether; vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono(meth)allyl ether, and polyethylene glycol mono(meth)allyl ether; Siloxane derivatives such as polydimethylsiloxane propylaminomaleic acid, polydimethylsiloxane aminopropylene aminomaleic acid, polydimethylsiloxane-bis-(propylaminomaleic acid), polydimethylsiloxane-bis-(dipropyleneaminomaleic acid), polydimethylsiloxane-(1-propyl-3-acrylate), polydimethylsiloxane-(1-propyl-3-methacrylate), polydimethylsiloxane-bis-(1-propyl-3-acrylate), and polydimethylsiloxane-bis-(1-propyl-3-methacrylate).

[0042] -Other monomers- When obtaining the polycarboxylic acid copolymer or a salt thereof, a monomer other than the monomers (I) to (IV) may be used as needed. That is, the polycarboxylic acid copolymer or a salt thereof may contain a constituent unit derived from a monomer other than the monomers (I) to (IV).

[0043] -Monomer ratio- When obtaining a polycarboxylic acid copolymer, the amount of monomer (I) used is usually 80 to 99% by weight, preferably 85 to 98% by weight, and more preferably 90 to 97% by weight. The amount of monomer (II) used is usually 0.1 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1 to 5% by weight. The amount of monomer (III) used is usually 0.1 to 20% by weight or 0.1 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1 to 5% by weight. The amount of monomer (IV) used is usually 0 to 18% by weight, preferably 0 to 15% by weight, and more preferably 0 to 12% by weight. The above amounts used are values ​​when the amounts of monomers (I) to (IV) used are taken as 100% by weight.

[0044] In the polycarboxylic acid copolymer or salt thereof (A), the ratio of the structure derived from the monomer (II) to the structure derived from the monomer (I) ((II) / (I)) is preferably 0.01 to 20% by weight, more preferably 0.1 to 18% by weight, and even more preferably 0.3 to 15% by weight. The ratio of the structure derived from the monomer (III) to the structure derived from the monomer (I) ((III) / (I)) is preferably 0.1 to 25% by weight, more preferably 1 to 15% by weight, and even more preferably 3 to 10% by weight. The ratio of the structure derived from the monomer (IV) to the structure derived from the monomer (I) ((IV) / (I)) is preferably 0 to 22% by weight, more preferably 0 to 20% by weight, and even more preferably 0 to 15% by weight. The ratio of the structure derived from the monomer (III) to the structure derived from the monomer (II) ( (III) / (II) ) is usually 35% by weight or more, preferably 40% by weight or more, and more preferably 45% by weight or more. The upper limit may be 99% by weight or less, and is usually 95% by weight or less or 90% by weight or less, preferably 80% by weight or less, and more preferably 70% by weight or less. Therefore, it is usually 35 to 99% by weight, preferably 40 to 95% by weight, more preferably 40 to 95% by weight, even more preferably 40 to 80% by weight, and even more preferably 40 to 70% by weight. The above ratios are usually the same as the amounts of each monomer added when producing the copolymer.

[0045] -Polymerization rate- The polymerization rate of each monomer is preferably 55% or more, more preferably 60% or more, even more preferably 70% or more, and even more preferably 80% or more. The polycarboxylic acid copolymer or its salt may contain unreacted monomers obtained by copolymerization of the above monomers, by-products during polymerization or production of each monomer (for example, water-soluble polyalkylene glycol having hydrogen atoms at both terminal groups (by-product derived from monomer (I)), one or two (co)polymers selected from monomers (I) to (IV), and three copolymers selected from monomers (I) to (IV) (lacking any of I to III)).

[0046] (1.2 Salt of polycarboxylic acid copolymer) The polycarboxylic acid copolymer may be in the form of a salt, such as a monovalent metal salt, a divalent metal salt, an ammonium salt, or an organic amine salt of the copolymer.

[0047] (1.3 Method for producing polycarboxylic acid copolymer or its salt) The polycarboxylic acid copolymer or a salt thereof may be produced by any method as long as it is a method of copolymerizing the above-mentioned monomers, such as polymerization in a solvent or bulk polymerization.

[0048] Examples of solvents used in polymerization in a solvent include water, lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as cyclohexane and n-hexane, esters such as ethyl acetate, and ketones such as acetone and methyl ethyl ketone. From the viewpoint of the solubility of the raw material monomers and the resulting copolymer, it is preferable to use one or more solvents selected from the group consisting of water and lower alcohols, and among these, it is more preferable to use water.

[0049] When copolymerization is carried out in a solvent, each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel, or a mixture of each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel. Alternatively, a solvent may be charged into a reaction vessel, and a mixture of the monomers and the solvent and a polymerization initiator solution may be continuously added dropwise to the reaction vessel, or a part or all of the monomers may be charged into a reaction vessel, and the polymerization initiator may be continuously added dropwise.

[0050] Polymerization initiators that can be used for copolymerization include, for example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and water-soluble organic peroxides such as t-butyl hydroperoxide when copolymerization is performed in an aqueous solvent. In this case, accelerators such as sodium bisulfite and Mohr's salt can also be used in combination. Furthermore, when copolymerization is performed in solvents such as lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, esters, or ketones, for example, peroxides such as benzoyl peroxide and lauryl peroxide; hydroperoxides such as cumene peroxide; and aromatic azo compounds such as azobisisobutyronitrile can be used as polymerization initiators. In this case, accelerators such as amine compounds can also be used in combination. Furthermore, when copolymerization is performed in a water-lower alcohol mixed solvent, the aforementioned polymerization initiators or combinations of polymerization initiators and accelerators can be appropriately selected and used. The polymerization temperature varies depending on polymerization conditions such as the solvent and polymerization initiator used, but is typically performed in the range of 50 to 120°C.

[0051] In the copolymerization, molecular weight can be adjusted, if necessary, using a chain transfer agent. Examples of chain transfer agents that can be used include known thiol compounds such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, and 2-mercaptoethanesulfonic acid; phosphorous acid, hypophosphorous acid, and salts thereof (e.g., sodium hypophosphite, potassium hypophosphite); sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, and salts thereof (e.g., sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite). These may be used alone or in combination. Furthermore, to adjust the molecular weight of the polycarboxylic acid copolymer or its salt (A), it is also effective to use a monomer (V) with higher chain transfer properties as a monomer for obtaining each of them. An example of a monomer (V) with high chain transfer properties is a (meth)allylsulfonic acid (salt) monomer. The content of the monomer (V) in the polycarboxylic acid copolymer or its salt (A) is usually 20% by weight or less, and preferably 10% by weight or less. The above content is calculated when the content of (A) is 100% by weight (the content of monomer (I) + the content of monomer (II) + the content of monomer (III) + the content of monomer (IV)).

[0052] When copolymerization is performed in an aqueous solvent to obtain a copolymer, the pH during polymerization typically becomes strongly acidic due to the influence of the monomers having unsaturated bonds. However, this can be adjusted to an appropriate pH. If pH adjustment is required during polymerization, the pH can be adjusted using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkyl phosphoric acid, alkyl sulfuric acid, alkyl sulfonic acid, or (alkyl)benzenesulfonic acid. Among these acidic substances, phosphoric acid is preferred due to its pH buffering effect. However, to eliminate the instability of the ester bonds in ester-based monomers, polymerization is preferably performed at a pH of 2 to 7. There are no particular limitations on the alkaline substance that can be used to adjust the pH, but alkaline substances such as NaOH and Ca(OH)2 are commonly used. pH adjustment can be performed on the monomers before polymerization or on the copolymer solution after polymerization. Alternatively, a portion of the alkaline substance can be added before polymerization, followed by polymerization and then further pH adjustment of the copolymer.

[0053] (1.5 Physical Properties of Polycarboxylic Acid Copolymer or Its Salt) -Weight average molecular weight- The weight-average molecular weight of the polycarboxylic acid copolymer or its salt is preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 20,000 or more. This can satisfactorily improve the dispersibility as an agricultural chemical additive. The upper limit is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 35,000 or less. This can suppress aggregation and avoid a decrease in workability. Therefore, the weight-average molecular weight is preferably 10,000 to 50,000, more preferably 15,000 to 40,000, and even more preferably 20,000 to 35,000.

[0054] -Mw / Mn- The molecular weight distribution (Mw / Mn) of the polycarboxylic acid copolymer or a salt thereof is preferably 1.2 to 3.0, more preferably 1.4 to 2.5, and even more preferably 1.5 to 2.0.

[0055] The weight average molecular weight in the present invention can be measured by a known method using gel permeation chromatography (GPC) in terms of polyethylene glycol.

[0056] Examples of GPC measurement conditions include the following: The weight average molecular weights in the examples below are values ​​measured under these conditions. Measuring device: Tosoh Columns used: Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ Eluent: 0.05 mM sodium nitrate / acetonitrile 8 / 2 (v / v) Standard material: polyethylene glycol (Tosoh, GL Science) Detector: Differential refractometer (manufactured by Tosoh) Calibration curve: polyethylene glycol standard

[0057] (2. Pesticide Additives) The pesticide additive contains the above-mentioned polycarboxylic acid copolymer or its salt (at least one type) as an active ingredient, which allows the additive to exhibit water surface spreading and dispersibility, and enables the functional components of the pesticide additive to be efficiently dispersed in liquid culture media (e.g., paddy field water, water for hydroponic cultivation).

[0058] (2.1 Target of pesticide additives (functional ingredients)) Examples of functional ingredients include active ingredients in pesticides and fertilizers. Pesticides include herbicides, insecticides, acaricides, nematicides, fungicides, bactericides, and other chemicals containing ingredients that can control or exterminate harmful organisms.

[0059] (2.2 Optional components) The agricultural chemical additive may contain optional components other than the polycarboxylic acid copolymer and its salt, as needed. Examples of optional components include excipients, colorants, preservatives, pH adjusters, stabilizers, disintegrants, carriers, binders, pH adjusters, antifoaming agents, nonionic surfactants, cationic surfactants, and amphoteric surfactants (formulation aids). The amount of optional components used is usually 0 to 30% by weight based on the lignin derivative or composition.

[0060] (2.3 Dosage form and manufacturing method) The dosage form of the pesticide additive is not particularly limited, and examples thereof include granules, particles, and liquid forms. Granules and particles can facilitate application. Liquid forms also facilitate mixing with functional ingredients, allowing the slurry to be stabilized after mixing. The pesticide additive may be formulated together with the functional ingredients, or may be formulated separately. An appropriate method for producing the pesticide additive can be selected depending on the dosage form.

[0061] (2.4 Usage amount and usage method) The amount of agricultural chemical additive added to the functional ingredient may be any effective amount, for example, 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.2 to 3% by weight, of the polycarboxylic acid copolymer or its salt relative to the total weight of the agricultural chemical or fertilizer formulation containing the functional ingredient. When the agricultural chemical additive is a formulation separate from the functional ingredient, it may be blended directly with the other ingredients (e.g., a granular agricultural chemical formulation) or may be dissolved in water and then added. For example, when the functional ingredient is slurried in water for use, adding the agricultural chemical additive to the slurry can stabilize the slurry and improve diffusion efficiency. [Example]

[0062] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, % means % by weight and parts means parts by weight unless otherwise specified.

[0063] Example 1 A glass reaction vessel equipped with a thermometer, stirrer, reflux device, and dropping device was charged with 99.3 parts of water and 100 parts of an ethylene oxide adduct of 3-methyl-3-buten-1-ol (average number of moles of ethylene oxide added: 57), and the temperature was raised to 40°C under stirring. After that, 1.6 parts of a 30% aqueous hydrogen peroxide solution was added, and then a monomer aqueous solution containing 6.0 parts of acrylic acid, 0.6 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 25), 10.3 parts of hydroxypropyl acrylate, and 30.4 parts of water, and a mixture of 0.2 parts of L-ascorbic acid, 0.7 parts of 3-mercaptopropionic acid, and 29.2 parts of water, were continuously added dropwise over two hours to the reaction vessel, which was maintained at 40°C. After the dropwise addition, the reaction was continued for another hour while maintaining the temperature.

[0064] The reaction vessel was then heated to 60°C, reacted for 1 hour, and then cooled to obtain an aqueous solution of the copolymer, which was copolymer (1) (weight average molecular weight 22,300, Mw / Mn 1.54).

[0065] Example 2 A glass reaction vessel equipped with a thermometer, stirrer, reflux device, nitrogen inlet tube, and dropping device was charged with 273.6 parts of water and 276 parts of an ethylene oxide adduct of 3-methyl-3-buten-1-ol (average number of moles of ethylene oxide added: 25). The reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 40°C under a nitrogen atmosphere. After that, 6.1 parts of a 30% aqueous hydrogen peroxide solution was added, and then a monomer aqueous solution containing 21.5 parts of acrylic acid, 3.3 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 25), 29.9 parts of hydroxypropyl acrylate, and 71.9 parts of water, and a mixture of 0.7 parts of L-ascorbic acid, 2.4 parts of 3-mercaptopropionic acid, and 101.9 parts of water, were continuously added dropwise over 2 hours to the reaction vessel, which was maintained at 40°C. After the dropwise addition, the reaction was continued for another 3 hours while maintaining the temperature.

[0066] The reaction vessel was then heated to 60°C, reacted for 1 hour, and then cooled to obtain an aqueous solution of the copolymer, which was copolymer (2) (weight average molecular weight 22,200, Mw / Mn 1.87).

[0067] Example 3 A glass reaction vessel equipped with a thermometer, stirrer, reflux device, and dropping device was charged with 1048.3 parts of water and 1056.0 parts of an ethylene oxide adduct of 3-methyl-3-buten-1-ol (average number of moles of ethylene oxide added: 57), and the temperature was raised to 40 ° C. under stirring. Then, 19.3 parts of a 30% aqueous hydrogen peroxide solution was added, followed by an aqueous monomer solution containing 63.4 parts of acrylic acid, 6.4 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 25), 143.1 parts of hydroxypropyl acrylate, and 286.0 parts of water, and a mixture of 2.1 parts of L-ascorbic acid, 7.8 parts of 3-mercaptopropionic acid, and 390.1 parts of water. Each solution was added dropwise over two hours to the reaction vessel, which was maintained at 40 ° C. After the dropwise addition, the reaction was continued for another hour while maintaining the temperature.

[0068] The reaction vessel was then heated to 60°C, reacted for 1 hour, and then cooled to obtain an aqueous solution of the copolymer, which was copolymer (3) (weight average molecular weight 25,500, Mw / Mn 1.53).

[0069] Example 4 A glass reaction vessel equipped with a thermometer, stirrer, reflux device, and dropping device was charged with 1073.2 parts of water and 1080.0 parts of an ethylene oxide adduct of 3-methyl-3-buten-1-ol (average number of moles of ethylene oxide added: 57), and the temperature was raised to 40°C under stirring. After that, 16.9 parts of a 30% aqueous hydrogen peroxide solution was added, and then a monomer aqueous solution containing 58.3 parts of acrylic acid, 6.5 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 25), 111.2 parts of hydroxypropyl acrylate, and 244.8 parts of water, and a mixture of 1.9 parts of L-ascorbic acid, 6.8 parts of 3-mercaptopropionic acid, and 391.3 parts of water, were continuously added dropwise over 2 hours to the reaction vessel maintained at 40°C. After the dropwise addition, the reaction was continued for another hour while maintaining the temperature.

[0070] The reaction vessel was then heated to 60°C, reacted for 1 hour, and then cooled to obtain an aqueous solution of the copolymer, which was copolymer (4) (weight average molecular weight 30,800, Mw / Mn 1.66).

[0071] Example 5 A glass reactor equipped with a thermometer, stirrer, reflux device, and dropping device was charged with 1072.7 parts of water and 1080.0 parts of an ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53), and the temperature was raised to 40°C under stirring. After that, 18.3 parts of a 30% aqueous hydrogen peroxide solution was added, and then a monomer aqueous solution containing 64.8 parts of acrylic acid, 6.5 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 25), 122.9 parts of hydroxypropyl acrylate, and 268.8 parts of water, and a mixture of 2.0 parts of L-ascorbic acid, 7.4 parts of 3-mercaptopropionic acid, and 390.6 parts of water, were continuously added dropwise over 2 hours to the reactor, which was maintained at 40°C. After the dropwise addition, the reaction was continued for another hour while maintaining the temperature.

[0072] The reaction vessel was then heated to 60°C, reacted for 1 hour, and then cooled to obtain an aqueous solution of the copolymer, which was copolymer (5) (weight average molecular weight 28,600, Mw / Mn 1.57).

[0073] Comparative Example 1 291 parts of water and 7 parts of polyethylene glycol monoallyl ether (average number of moles of ethylene oxide added: 10) were added to a glass reaction vessel equipped with a thermometer, stirrer, reflux device, nitrogen inlet tube, and dropping device, and the atmosphere in the reaction vessel was replaced with nitrogen while stirring. After heating to 100°C under a nitrogen atmosphere, a monomer aqueous solution containing 4 parts of methacrylic acid, 0.1 parts of acrylic acid, 22 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 25), 36 parts of hydroxypropyl acrylate, and 33 parts of water, and a mixture of 1 part of ammonium persulfate and 44 parts of water, were added dropwise over 2 hours to the reaction vessel, which was maintained at 100°C. After the addition, the temperature was maintained at 100°C and the reaction was continued for another hour to obtain an aqueous copolymer solution. The pH of this solution was adjusted to 4 with a 30% NaOH aqueous solution to obtain copolymer (6) (weight average molecular weight: 22,000, Mw / Mn: 2.10).

[0074] [Table 1]

[0075] (Notes in Table 1) MA: methacrylic acid AA: acrylic acid HPEG: a compound of formula (1) (ethylene oxide adduct of methallyl alcohol: R 1 is a methallyl group, A 1 is an ethyl group, n1 is 53, R 2 is a hydrogen atom) TPEG: a compound of formula (1) (ethylene oxide adduct of 3-methyl-3-buten-1-ol: R 1 is a 3-methyl-3-buten-1-ol group, A 1 is an ethyl group, n1 is 25 or 57, R 2 is a hydrogen atom) HPA: a compound of formula (2) (2-hydroxypropyl acrylate: R 3 , R 4 , R 5 is a hydrogen atom, m is 0, A 2 is a propyl group (-CH2CH(CH2)-), n2 is 1, and X is a hydrogen atom MPEG-MA: a compound of formula (2) (R 3 , R 4 is a hydrogen atom, R 5 is a methyl group, m is 0, A 2 is an ethyl group, n2 is 25, and X is a hydrogen atom) PEG-AL: Compound of formula (1) (methoxypolyethylene glycol methacrylate: polyethylene glycol monoallyl ether: R 1 is an allyl group, A 1 is an ethyl group, n1 is 10, R 2 is a hydrogen atom) BMPA: β-mercaptopropionic acid (3-mercaptopropionic acid)

[0076] (Wettability test) 0.1 g of calcium stearate was weighed out using a precision balance and placed in a tablet press, where it was compacted and molded under conditions of 20 MPa for 1 minute to obtain a calcium stearate molded sheet (final weight: 0.09 ± 0.002 g). A rectangular plastic container (10 cm long, 40 cm wide) was filled with distilled water with a hardness of 0.4, and the calcium stearate molded sheet was floated as a lump on the surface of the water near the center of the plastic container.

[0077] Then, the sample aqueous solution (concentration: 0.1 wt%) was gently dropped onto the edge of the plastic container, and the spreading ability of the calcium stearate molded sheet on the water surface (the distance from the position of the molded sheet before the sample was dropped to the position to which it moved after the sample was dropped: spreading distance (cm)) was measured (Table 2).

[0078] [Table 2]

[0079] It was found that the samples of Examples 1 to 5 had a longer spreading distance and exhibited high spreading properties compared to Comparative Example 1 (Table 2). This result indicates that the pesticide additive of the present invention can exhibit good spreading properties and dispersion stability.

Claims

1. 80 to 99% by weight of a monomer (I) represented by the following general formula (1), 0.1 to 10% by weight of a monomer (II) represented by the following general formula (2), 0.1 to 20% by weight of an unsaturated monocarboxylic acid monomer (III), and Other monomers (IV) copolymerizable with the monomers (I) to (III) 0 to 18% by weight is a copolymer of The monomer (II) includes a monomer (IIa) in which n2 in the general formula (2) is 1 to 3 and a monomer (IIb) in which n2 in the general formula (2) is 4 to 100, the weight ratio of the monomer (IIa) to the monomer (IIb) ((IIa) / (IIb)) is in the range of 60 / 40 to 99 / 1; A pesticide additive containing a polycarboxylic acid copolymer or a salt thereof. 【Chemistry 1】 (In the formula, R 1 represents an allyl group, a methallyl group, or a residue of 3-methyl-3-buten-1-ol. 1 O's may be the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. n1 is the average number of moles of oxyalkylene groups added and represents a number from 1 to 100. R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 【Chemistry 2】 (In the formula, R 3 , R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m represents a number from 0 to 2. 2 O's are the same or different and represent oxyalkylene groups having 2 to 18 carbon atoms. n2 is the average number of moles of oxyalkylene groups added and represents a number from 1 to 100. X represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

2. 2. The agricultural chemical additive according to claim 1, wherein the ratio of the structure derived from the monomer (III) to the structure derived from the monomer (II) ((III) / (II)) is 35 to 99% by weight.

3. The agricultural additive according to claim 1 or 2, wherein the monomer (III) comprises acrylic acid or a salt thereof (IIIa) and methacrylic acid or a salt thereof (IIIb).

4. The ratio ((IIIa) / (IIIb) of the structure derived from acrylic acid or a salt thereof (IIIa) to the structure derived from methacrylic acid or a salt thereof (IIIb) is (99% to 51%) / (1% to 49%). The agricultural chemical additive according to claim 3.

5. The agricultural chemical additive according to any one of claims 1 to 4, having a weight average molecular weight of 10,000 to 50,000.

6. The pesticide additive according to any one of claims 1 to 5, wherein the molecular weight distribution is 1.2 to 3.

0.

7. The pesticide additive according to any one of claims 1 to 6, which is for use in granular pesticides.

8. The pesticide additive according to any one of claims 1 to 6, which is for use in liquid pesticides.

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